The invention relates to new benzoylurea compounds and to a method of preparing said compounds. The invention also relates to compositions having insecticidal and acaricidal activity and comprising these compounds, and to the use of said compositions for controlling insects and/or mites.
It is already known that certain N-benzoyl-N'-phenylurea compounds have an insecticidal activity. From Netherlands patent application No. 7105350 in the name of Applicants it appears that in particular the substitution pattern of the benzoyl group has an important influence on said activity. In general, a high insecticidal activity is found in benzoylurea compounds the benzoyl group of which is substituted in the 2- or 2,6-positions, for example, with one or two halogen atoms. Substituents on the other side of the molecule, so in the N'-phenyl ring, are less essential for the insecticidal activity but can nevertheless influence said activity in such manner that the benzoylurea compound is better or worse suitable for practical applications. For example, it appears from an article by Wellinga et al. in J. Arg. Food Chem., Vol. 21, No. 3, 1973, pp. 348-354 that electrons-donating substituents at the N'-phenyl ring, for example, a methoxy group, adversely influence the insecticidal activity.
It has surprisingly been found, that N'-phenyl benzoylurea compounds, to the phenyl group of which are attached via an oxygen bridge, an oxycarbonyl bridge, an oxycarbonylamino bridge or an alkoxy bridge a whether or not substituted cycloalkyl or cycloalkenyl group or a bi- or polycyclic hydrocarbyl group, have an interesting insecticidal activity. Moreover, an acaricidal activity is also found in the new benzoylurea compounds according to the invention.
Chemically related benzoylurea compounds are described in the Netherlands patent application No. 7905155 in the name of Applicants, e.g. N-(2-chlorobenzoyl)-N'-[4-(1-phenylcyclohexyloxy)phenyl]urea.
As will be clear from the Examples, this known compound is considerably less active than the new compounds of the present invention.
The invention relates to benzoylurea compounds of the general formula ##STR3## wherein R.sub.1 is a hydrogen atom or represents 1 or 2 halogen atoms;
Ar is a para-phenylene group or a para-pyridylene group, which groups may be substituted with 1 or 2 substituents selected from the group consisting of chlorine, methyl and trifluoromethyl; PA0 B is an oxygen atom or represents a group having the formula ##STR4## wherein R.sub.2 is a hydrogen atom or an alkyl group having 1-4 carbon atoms; and PA0 R is a cycloalkyl group or a cycloalkenyl group having 6-12 carbon atoms, which groups may be substituted with 1-3 substituents selected from the group consisting of alkyl and alkenyl having 1-6 carbon atoms, or wherein PA0 R is a bi- or polycyclic, saturated or unsaturated, hydrocarbyl group, having 8-14 carbon atoms and, if desired, substituted with 1-3 substituents selected from the group consisting of alkyl and alkenyl having 1-6 carbon atoms; PA0 if Ar is a whether or not substituted para-phenylene group, and PA0 R is a whether or not substituted cyclohexyl group, or a saturated bi- or polycyclic hydrocarbyl group having 8-14 carbon atoms, then B does not represent an oxygen atom. PA0 R.sub.3 is a hydrogen atom or a halogen atom, PA0 R.sub.4 is a halogen atom, PA0 R.sub.5 represents 1-3 alkyl or alkenyl groups having 1-6 carbon atoms, and PA0 R.sub.6 is a hydrogen atom or represents 1 or 2 substituents selected from the group consisting of chlorine, methyl and trifluoromethyl, PA0 (1) N-(2-chlorobenzoyl)-N'-(2-l-menthyloxy-5-pyridyl)urea, PA0 (2) N-(2,6-difluorobenzoyl)-N'-(2-l-menthyloxy-5-pyridyl)urea, PA0 (3) N-benzoyl-N'-(4-dl-menthyloxycarbonylphenyl)urea, PA0 (4) N-(2-chlorobenzoyl)-N'-(4-dl-menthyloxycarbonylphenyl)urea, PA0 (5) N-(2,6-difluorobenzoyl)-N'-(4-dl-menthyloxycarbonylphenyl)urea PA0 (6) N-(2-chlorbenzoyl)-N'-(4-dl-menthyloxycarbonylaminophenyl)urea, PA0 (7) N-(2,6-difluorobenzoyl)-N'-(4-dl-menthyloxycarbonylaminophenyl)urea, PA0 (8) N-(2,6-difluorobenzoyl)-N'-(4-cyclododecyloxyphenyl)urea, PA0 (9) N-(2,6-difluorobenzoyl)-N'-(4-myrtenyloxyphenyl)urea, PA0 (10) N-(2,6-difluorobenzoyl)-N'-[4-(2-isopropylcyclohexyloxycarbonyl)phenyl]ure a, PA0 (11) N-(2-chlorobenzoyl)-N'-[4-(2-isopropylcyclohexyloxycarbonyl)phenyl]urea, PA0 (12) N-(2-chlorobenzoyl)-N'-[4-(3,5,5-trimethylcyclohexen-2-yloxy)phenyl]urea, PA0 (13) N-(2,6-difluorobenzoyl)-N'-[4-(3,5,5-trimethylcyclohexen-2-yloxy)phenyl]ur ea, PA0 (14) N-(2-chlorobenzoyl)-N'-[4-(1-cyclohexyl-n-butoxy)phenyl]urea, PA0 (15) N-(2,6-difluorobenzoyl)-N'-[4-(1-cyclohexyl-n-butoxy)phenyl]urea, PA0 (16) N-(2-chlorobenzoyl)-N'-[4-(1-cyclohexyl-2-methyl-n-propoxy)phenyl]urea, PA0 (17) N-(2,6-difluorobenzoyl)-N'-[4-(1-cyclohexyl-2-methyl-n-propoxy)phenyl]urea PA0 (18) N-(2-chlorobenzoyl)-N'-[3,5-dichloro-4-(1-cyclohexyl-n-butoxy)phenyl]urea, and PA0 (19) N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-(1-cyclohexyl-n-butoxy)phenyl]u rea. PA0 1. organic chlorine compounds, for example 6,7,8,9,10,10-hexachloro-1,5,5a,6,9a-hexahydro-6,9-methano-2,4,3-benzo[e]- dioxathiepine-3-oxide; PA0 2. carbamates, for example, 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethyl carbamate and 2-isopropoxyphenyl methylcarbamate; PA0 3. di(m)ethylphosphates, for example, 2-chloro-2-diethylcarbamoyl-1-methylvinyl-, 2-methoxycarbonyl-1-methylvinyl-, 2-chloro-1-(2,4-dichlorophenyl)vinyl-, and 2-chloro-1-(2,4,5-trichlorophenyl)vinyl di(m)ethylphosphate; PA0 4. O,O-di(m)ethyl phosphorothioates, for example, O(S)-2-methylthioethyl-, S-2-ethylsulphinylethyl-, S-2-(1-methylcarbamoylethylthio)ethyl-, O-4-bromo-2,5-dichlorophenyl-, O-3,5,6-trichloro-2-pyridyl-, O-2-isopropyl-6-methylpyrimidin-4-yl-, and O-4-nitrophenyl O,O-di(m)ethyl phosphorothioate; PA0 5. O,O-di(m)ethyl phosphorodithioates, for example, S-methylcarbamoylmethyl-, S-2-ethylthioethyl-, S-(3,4-dihydro-4-oxobenzo[d]-1,2,3-triazin-3-ylmethyl)-, S-1,2-di(ethoxycarbonyl)ethyl-, S-6-chloro-2-oxobenzoxazolin-3-ylmethyl-, and S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-di(m)ethylphosphorodithioate; PA0 6. phosphonates, for example, dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate; PA0 7. natural and synthetic pyrethroids; PA0 8. amidines, for example, N'-(2-methyl-4-chlorophenyl)-N,N-dimethylformamidine; PA0 9. microbial insecticides, such as Bacillus thuringiensis; PA0 10. carbamoyl-oximes, such as S-methyl N-(methylcarbamoyloxy)thioacetamidate; and PA0 11. other benzoylurea compounds, such as N-(2,6-difluorobenzoyl)-N'-(4-chlorophenyl)urea. PA0 1. organic tin compounds, for example, tricyclohexyl tin hydroxide and di[tri-(2-methyl-2-phenylpropyl)tin]oxide; PA0 2. organic halogen compounds, for example isopropyl 4,4'-dibromobenzilate, 2,2,2-trichloro-1,1-di(4-chlorphenyl)ethanol and 2,4,5,4'-tetrachlorodiphenyl sulphone; PA0 3. synthetic pyrethroids, PA0 1. organic tin compounds, for example, triphenyl tin hydroxide and triphenyl tin acetate; PA0 2. alkylene bisdithiocarbamates, for example, zinc ethylenebisdithiocarbamate and manganese ethylene bisdithiocarbamate; PA0 3. 1-acyl- or 1-carbamoyl-N-benzimidazole (-2) carbamates and 1,2-bis(3-alkoxycarbonyl-2-thiureido)benzene;
with the proviso, that,
These compounds have an interesting insecticidal and acaricidal activity as will become apparent from the examples.
Benzoylurea compounds of the general formulae ##STR5## wherein R.sub.1 has the above meaning,
are to be preferred on account of their high insecticidal activities.
Various compounds of the invention may occur in two stereoisomers, namely the d- and the l-form, while of course mixtures of these stereoisomers are also possible. If desired, the stereoisomers can be separated from each other by methods known for this purpose, but for practical considerations the use of a sterically pure starting material is to be preferred for the preparation of one of the stereoisomers in a pure form.
Examples of new benzoylurea compounds according to the invention are:
Related benzoylurea compounds are the subject of the non-prepublished European patent application No. 832018634 in the name of the Applicant.
The substances according to the invention may be used for the control of insects in agriculture and horticulture, in forests and in surface water, as well as for the protection of textile against attack by, for example, moths and carpet beetles, against insects in stocks, for example, in stored cereals, and against insects in the veterinary and medical-hygienic sectors.
The substances according to the invention may also be used for the control of insects living in the manure of warm-blooded animals, such as cows, pigs and hens. For this application the active compounds can be administered orally to the animals, for example, mixed through the food, so that they land in the manure after some time ("through-feeding").
The compounds according to the invention are particularly active against larvae and eggs of insects. In principle, the compounds may be used against all insects mentioned in Pestic. Sci. 9, 373-386 (1978).
For practical pesticidal application the substances in accordance with the invention are usually processed in compositions. In such compositions the active substance is mixed with solid carrier material or dissolved or dispersed in liquid carrier material, if desired in combination with auxiliary substances, for example, emulsufiers, wetting agents, dispersible agents and stabilizers.
Examples of compositions according to the invention are aqueous solutions and dispersions, oily solutions and oily dispersions, solutions in organic solvents, pastes, dusting powders, dispersible powders, miscible oils, granules, pellets and aerosol compositions.
Dispersible powders, pastes and miscible oils are compositions in concentrate form which are diluted prior to or during use.
The invert emulsions and solutions in organic solvents are mainly used in air application, namely when large areas are treated with a comparatively small quantity of composition. The invert emulsion can be prepared shortly before or even during spraying in the spraying apparatus be emulsifying water in an oily solution or an oily dispersion of the active substance. The solutions of the active substance in organic solvents may be provided with a phytotoxicity-reducing substance, for example, wool fat, wool fatty acid or wool fatty alcohol.
A few forms of compositions will be described in more detail hereinafter by way of example.
Granular compositions are prepared by taking up, for example, the active substance in a solvent or dispersing it in a diluent and impregnating the resulting solution/suspension, if desired in the presence of a binder, on granular carrier material, for example porous granules (for example pumice and attaclay), mineral non-porous granules (sand or ground marl), organic granules (for example, dried coffee grounds, cut tobacco stems or ground corncobs). A granular composition can also be prepared by compressing the active substance together with powdered minerals in the presence of lubricants and binders and disintegrating the compressed product to the desired grain size and sieving it. Granular compositions can be prepared in a different manner by mixing the active substance in powder form with powdered fillers, and glomulating the mixture then with liquid to the desired particle size.
Dusting powders can be obtained by intimately mixing the active substance with an inert solid powdered carrier material, for example, talcum.
Dispersable powders are prepared by mixing 10 to 80 parts by weight of a solid inert carrier, for example kaolin, dolomite, gypsum, chalk, bentonite, attapulgite, colloidal SiO.sub.2 or mixtures of these and similar substances, with 10 to 80 parts by weight of the active substance, 1 to 5 parts by weight or a dispersing agent, for example the lignine sulphonates or alkylnaphthalene sulphonates known for this purpose, preferably also 0.5 to 5 parts by weight of a wetting agent, for example, fatty alcohol sulphates, alkyl aryl sulphonates, fatty acid condensation products, or polyoxyethylene compounds, and finally, if desired, other additives.
For the preparation of miscible oils the active compound is dissolved in a suitable solvent which preferably is poorly water-miscible, and one or more emulsifiers are added to this solution. Suitable solvents are, for example, xylene, toluene, petroleum distillates which are rich in aromates, for example, solvent naphtha, distilled tar oil and mixtures of these liquids. As emulsifiers may be used, for example, polyoxyethylene compounds and/or alkyl aryl sulphonates. The concentration of the active compound in these miscible oils is not restricted to narrow limits and may vary, for example, between 2 and 50% by weight.
In addition to a miscible oil may also be mentioned as a liquid and highly concentrated primary composition a solution of the active substance in a readily water-miscible liquid, for example, a glycol, a glycol ether, dimethylformamide, or N-methylpyrrolidone, to which solution a dispersing agent, and if desired, a surface-active substance has been added. When diluting with water shortly before or during spraying, an aqueous dispersion of the active substance is then obtained.
An aerosol composition according to the invention is obtained in the usual manner by incorporation the active substance, if desired in a solvent, in a volatile liquid to be used as a propellant, for example, a mixture of chlorine-fluorine derivatives of methane and ethane, a mixture of lower hydrocarbons, dimethyl ether, or gases such as carbon dioxide, nitrogen and nitrous oxide.
Fumigating candles or fumigating powders, i.e. compositions which, while burning, can generate a pesticidal smoke, are obtained by taking up the active substance in a combustible mixture which may contain as a fuel a sugar or a wood, preferably in a ground form, a substance to maintain combustion, for example, ammonium nitrate or potassium chlorate, and furthermore a substance to delay combustion, for example, kaolin, bentonite and/or colloidal silicic acid.
In addition to the above-mentioned ingredients, the agents according to the invention may also contain other substances known for use in this type of agents. For example a lubricant, e.g., calcium stearate or magnesium stearate, may be added to a dispersible powder or a mixture to be granulated. "Adhesives", for example, polyvinylalcohol, cellulose derivatives or other colloidal materials, such as casein, may also be added so as to improve the adhesion of the pesticide to the crop. Furthermore, a substance may be added to reduce the phytotoxicity of the active substance, carrier material or auxiliary substance, for example, wool fat or wool fatty alcohol.
Pesticidal compounds known per se may also be incorporated in the compositions according to the invention. As a result of this the activity spectrum of the composition is widened and synergism may occur.
For use in such a combination composition are to be considered the following known insecticidal, acaricidal and fungicidal compounds:
Insectides, for example:
Acaricides, for example:
and furthermore: 3-chloro-.alpha.-ethoxyimino-2,6-dimethoxybenzyl benzoate and O,O-dimethyl S-methylcarbamoyl methyl phosphorothioate.
Fungicides, for example:
and furthermore 2,4-dinitro-6-(2-octylphenylcrotonate); 1-[bis(dimethylamino)phosphoryl]-3-phenyl-5-amino-1,2,4-triazole; N-trichloromethylthiophthalimide; N-trichloromethylthiotetrahydrophthalimide; N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide; N-dichlorofluoromethylthio-N-phenyl-N,N'-dimethylsulphamide; tetrachloroisophthalonitrile; 2-(4'-thiazolyl)benzimidazole; 5-butyl-2-ethylamino-6-methylpyrimidine-4-yl-dimethylsulphamate; 1-(4-chlorophenoxy)-3,3-dimethyl-1(1,2,4-triazole-1-yl)-2-butanone; .alpha.-(2-chlorophenyl)-.alpha.-(4-chlorophenyl)-5-pyrimidinemethanol; 1-(isopropylcarbamoyl)-3-(3,5-dichlorophenyl)hydantoin; N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1,2-carboximide; N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboximide; N-tridecyl-2,6-dimethylmorpholine; metal salts of ethylphosphite; and N-(2,6-dimethylphenyl-N-methoxyacetyl)alanine methylester; or mixtures of these compounds.
The dosage of the insecticidal composition according to the invention desired for practical application will, of course, depend on various factors, for example, application area, selected active material, composition form, nature and extent of the infection, and the weather conditions.
In general it holds that favourable results are achieved with a dosage which corresponds to 1 to 5,000 g of the active substance per hectare.
For the above-described "through-feeding" the active substance is mixed through the food in a quantity which is effective for insecticidal applications.
The compounds according to the invention are novel substances which can be prepared in a manner known per se for related compounds.
For example, the compounds according to the invention can be prepared by reacting a substituted aniline of the general formula EQU R--B--Ar--NH.sub.2
wherein R, B and Ar have the above meanings, with a benzoylisocyanate of the general formula ##STR6## wherein R.sub.1 also has the above meaning.
The novel compounds according to the invention can also be prepared by reacting a substituted benzamide of the general formula ##STR7## wherein R.sub.1 has the above meaning, with an isocyanate of the general formula EQU R--B--Ar--NCO
wherein R.sub.1, B and Ar also have the above meanings.
The above reactions are preferably carried out in the presence of an organic solvent, for example, an aromatic hydrocarbon, an alkyl halide, a cyclic or non-cyclic dialkyl ether, or acetonitrile, at a reaction temperature between 0.degree. C. and the boiling-point of the solvent used.
Although the above-indicated methods of preparation are the best suitable, the novel compounds may also be prepared in a different way, for example, as described in the above-mentioned Netherlands patent application No. 7105350 or according to the methods described in Netherlands patent application No. 7806678 or No. 8005588.
The invention will now be described in greater detail with reference to the ensuing specific examples.